JP6493876B2 - Ink binder composition, ink binder, ink material set and ink - Google Patents

Description

  The present invention relates to an ink binder composition, an ink binder, an ink material set, and an ink.

  Decorated injection molded products are used for members of automobiles, electrical appliances, mobile phones such as smartphones, and mobile terminals. These injection-molded products are, for example, formed a decorative film by forming an ink layer by printing ink containing a resin on the back surface of a transparent film, and the decorative film has a curved surface, unevenness or flat shape by compression molding After being processed into a mold, it is mounted on a mold, injected with a molten resin toward the ink surface of the decorative film, and manufactured by injection molding in which the resin surface and the decorative film are integrated.

  In addition, the ink layer of the decorative film comes into contact with a molten high-temperature resin during injection molding, or is held in a mold heated to a high temperature of about 200 ° C. to 300 ° C. Exposed to. Therefore, the ink used for forming the ink layer of the decorative film has a high heat resistance without causing an ink flow, which is a phenomenon in which the ink layer flows even when exposed to a high temperature. It is required to have

  Since the heat resistance of the ink depends on the heat resistance of the resin used in the ink, an ink using a polycarbonate resin having excellent heat resistance has been developed. For example, a heat-resistant printing ink using a polycarbonate resin as a binder resin is known (for example, see Patent Document 1).

  However, since the polycarbonate resin has a problem that it is inferior in weather resistance, an ink using an acrylic resin excellent in weather resistance has been developed. For example, an ink using poly (meth) acrylate having a Vicat softening temperature VST (ISO 306B) of at least 115 ° C. as a binder is known (for example, see Patent Document 2).

  Further, as an ink printed on a food tray film, an ink containing a binder resin and a metal chelate compound as a crosslinking agent has been developed. For example, an acrylic resin such as an alkyl methacrylate-methacrylate copolymer, an alkyl methacrylate-methacrylate ester-styrene copolymer resin, a metal chelate compound such as a titanium chelate compound, and a polyester polyol compound having an epoxy group The printing ink composition containing is known (for example, refer patent document 3).

  In addition, high-intensity specular screen inks have been developed that are used for the production of printed matter having a specular gloss or a color specular gloss and are excellent in screen printability. For example, a high-intensity specular screen ink containing a binder component such as vapor-deposited aluminum foil pigment, polyester, poly (meth) acrylate, and an aluminum chelate compound is known (see, for example, Patent Document 4).

  Furthermore, a glittering paint composition has been developed that can obtain a coating film in which a glittering pigment obtained by pulverizing a vapor-deposited metal film into a metal piece is oriented in a planar shape. For example, an acrylic resin having a glass transition temperature of 0 to 45 ° C., a hydroxyl value of 20 to 80 mg KOH / g, and a weight average molecular weight (Mw) of 200,000 to 1,000,000, a curing agent such as a melamine resin, and a deposited metal film A glittering paint composition containing a glittering pigment obtained by pulverizing the powder into a metal piece and a solvent is known (see, for example, Patent Document 5).

JP 2004-67838 A JP-T-2005-501161 JP 2004-285245 A JP 2008-138193 A JP 2006-169416 A

  However, since the heat-resistant printing ink described in Patent Document 1 uses a polycarbonate resin, there is a problem that the weather resistance is poor. In addition, in the ink described in Patent Document 2, an acrylic resin having a high softening temperature is used in order to improve heat resistance. However, an acrylic resin having a high softening temperature tends to be hard and brittle. In a film having an ink layer formed by using a film, there is a possibility that a crack may occur in the ink layer when the film is bent and stretched during processing by compression molding, and the processability is poor.

  In the printing ink composition described in Patent Document 3, an acrylic resin such as an alkyl methacrylate-methacrylic acid ester copolymer or an alkyl methacrylate-methacrylic acid ester-styrene copolymer resin is used as a binder resin. When an ink layer is formed using these resins, there is a problem that the elasticity and viscosity of the ink layer at a high temperature are insufficient and heat resistance and workability are poor. Furthermore, in the high-intensity specular screen ink described in Patent Document 4, polyester, poly (meth) acrylic acid ester, or the like is used as a binder component. When an ink layer is formed using polyester, the ink layer is heat resistant. Therefore, when an ink layer is formed using poly (meth) acrylic acid ester, although heat resistance is improved, it is not sufficient in terms of suppressing ink flow, and processability is also improved. There is a problem that it is inferior.

  Moreover, in the glittering paint composition of patent document 5, although hardening agents, such as an acrylic resin and a melamine resin, are used, when forming a coating film using these, it is compatible with heat resistance and workability. In particular, the coating film becomes too hard and the processability is poor.

  The present invention has been made in view of the above problems, and has an ink binder composition, an ink binder, and an ink material that are excellent in heat resistance and excellent in workability during compression molding when an ink layer is formed. The object is to provide a set and ink.

Means for solving the above problems include the following embodiments.
<1> Structural unit derived from (meth) acrylic acid alkyl ester (A), structural unit derived from monomer having carboxy group (B), and structural unit derived from monomer having polar functional group other than carboxy group ( C), the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more based on the total structural units, and the content of the structural unit (B) and The (meth) acrylic polymer having a total content of the structural unit (C) of 8 mol% or more with respect to all the structural units and a glass transition temperature of 20 ° C. or higher, and the (meth) acrylic polymer The binder composition for inks containing 2 mass parts-20 mass parts metal chelate compound with respect to 100 mass parts.
<2> The ink binder composition according to <1>, wherein the content ratio of the structural unit (C) to the structural unit (B) is 0.5 to 2.0 on a molar basis.
<3> The ink binder composition according to <1> or <2>, wherein the metal chelate compound is an aluminum chelate compound.
<4> The ink binder composition according to <3>, wherein the aluminum chelate compound is aluminum monoacetylacetonate bis (ethylacetoacetate).
<5> The (meth) acrylic acid alkyl ester has a glass transition temperature of -40 ° C. or lower when the homopolymer is used and a glass transition temperature of 50 ° C. or higher when the (meth) acrylic acid alkyl ester and the homopolymer are used. The ink binder composition according to any one of <1> to <4>, comprising (meth) acrylic acid alkyl ester.
<6> The ink binder composition according to any one of <1> to <5>, including a monomer having an amino group as a monomer having a polar functional group other than the carboxy group.
<7> The binder composition for ink according to any one of <1> to <6>, wherein the glass transition temperature of the (meth) acrylic polymer is 60 ° C. or lower.

  <8> Structural unit derived from (meth) acrylic acid alkyl ester (A), structural unit derived from monomer having carboxy group (B), and structural unit derived from monomer having polar functional group other than carboxy group ( C), and the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more based on the total structural units, and the content of the structural unit (B) And the sum total of the content rate of the said structural unit (C) is 8 mol% or more with respect to all the structural units, and is used for injection molding containing the (meth) acrylic-type polymer whose glass transition temperature is 20 degreeC or more. Ink binder.

  <9> Structural unit derived from (meth) acrylic acid alkyl ester (A), structural unit derived from monomer having carboxy group (B), and structural unit derived from monomer having polar functional group other than carboxy group ( C), and the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more based on the total structural units, and the content of the structural unit (B) And a first material containing a (meth) acrylic polymer having a total content of the structural unit (C) of 8 mol% or more with respect to all the structural units and a glass transition temperature of 20 ° C. or higher; And a second material containing a metal chelate compound.

<10> The first material and the second material in the ink binder composition according to any one of <1> to <7> or the ink material set according to <9>, and an organic solvent And ink containing.
<11> The ink according to <10>, further containing a colorant.
<12> The ink according to <10> or <11>, which is used for a film for injection molding.

  According to the present invention, it is possible to provide an ink binder composition, an ink binder, an ink material set, and an ink that are excellent in heat resistance when forming an ink layer, and further excellent in workability during compression molding. .

Embodiments that are examples of the present invention will be described below. In addition, the numerical value range shown using "to" in this specification shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. In addition, in the present specification, the amount of each component in the composition means the total amount of a plurality of types of substances corresponding to the component, unless a specific case is used in combination of a plurality of types of substances corresponding to the respective components. To do.
Furthermore, (meth) acryl means at least one of acryl and methacryl.
Furthermore, (meth) acrylate means at least one of acrylate and methacrylate.
Furthermore, the ink binder composition is a composition before the crosslinking reaction between the (meth) acrylic polymer and the metal chelate compound is completed, and means, for example, a liquid, paste or powder composition.
Furthermore, the ink layer is a layer after the crosslinking reaction between the (meth) acrylic polymer and the metal chelate compound is completed, and means, for example, a solid layer. The ink layer may be a colored layer containing a colorant such as a pigment or a dye, or may be a non-colored layer.

[Binder composition for ink]
The ink binder composition in the present invention has a structural unit (A) derived from a (meth) acrylic acid alkyl ester, a structural unit (B) derived from a monomer having a carboxy group, and a polar functional group other than the carboxy group. The structural unit (C) derived from the monomer, the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more with respect to all the structural units, and the structural unit (B) The (meth) acrylic polymer having a total content of 8% and a total content of structural units (C) of 8 mol% and a glass transition temperature of 20 ° C. 2 parts by mass to 20 parts by mass of a metal chelate compound with respect to 100 parts by mass of the acrylic polymer.

  The ink binder composition in the present invention is preferably used for injection molding. For example, when manufacturing an injection molded product used as a member of a mobile phone such as an automobile, an electrical appliance, a smartphone, or a mobile terminal. Used for. Specifically, the injection-molded product forms an ink layer by printing the ink containing the ink binder composition of the present invention on the back surface of the transparent film to form a decorative film, and the decorative film is compression-molded. Injection molding that integrates the resin surface and the decorative film by injecting the molten resin toward the ink surface of the decorative film after processing into a shape having a curved surface, unevenness or flat surface Manufactured by.

  The ink binder composition in the invention includes a structural unit (B) derived from a monomer having a carboxy group and a structural unit (C) derived from a monomer having a polar functional group other than a carboxy group, and the structural unit (B ) And the content of the structural unit (C) are each 3 mol% or more with respect to all the structural units, and the sum of the content of the structural unit (B) and the content of the structural unit (C) is A (meth) acrylic polymer in an amount of 8 mol% or more based on the total structural units is included. A polar functional group (B) derived from a monomer having a carboxy group which is a reaction point with the metal chelate compound and a reactivity with the metal chelate compound lower than that of the carboxy group or not reacting with the metal chelate compound ( The structural unit (C) derived from a monomer having a polar functional group other than a carboxy group) is contained in a predetermined amount in the (meth) acrylic polymer, so that when the ink layer is formed, the elasticity at high temperatures and Both viscosities can be increased, and both heat resistance and workability can be achieved.

  Specifically, in the (meth) acrylic polymer, the content of the structural unit (B) is 3 mol% or more with respect to all the structural units, thereby sufficiently securing the reaction point with the metal chelate compound. Therefore, the crosslink density at the time of crosslinking can be increased to suppress the occurrence of ink flow. Therefore, it is possible to provide an ink binder composition having excellent heat resistance when an ink layer is formed.

  Furthermore, when the content of the structural unit (C) in the (meth) acrylic polymer is 3 mol% or more with respect to the total structural units, the viscosity becomes high when the ink layer is formed, and at the time of compression molding The processability is excellent, and the occurrence of cracks in the ink layer can be suppressed. Furthermore, the adhesion between the ink layer and the substrate to be printed such as a transparent film can be improved, and peeling from the substrate to be printed can be suppressed.

  In addition, the sum of the content of the structural unit (B) and the content of the structural unit (C) in the (meth) acrylic polymer is 8 mol% or more with respect to all the structural units, thereby forming an ink layer. In this case, both elasticity and viscosity at high temperature can be increased, and both heat resistance and workability can be achieved.

  In the present specification, the total structural unit means the total of the structural units derived from the structural unit (A), the structural unit (B), the structural unit (C), and other copolymerizable monomers.

  The (meth) acrylic polymer used in the present invention has a glass transition temperature (Tg) of 20 ° C. or higher. When the glass transition temperature is 20 ° C. or higher, the occurrence of ink flow can be suppressed and heat resistance is excellent.

  The binder composition for ink in the present invention contains a metal chelate compound together with a (meth) acrylic polymer, and the content of the metal chelate compound is 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. Part.

  By cross-linking a (meth) acrylic polymer using a metal chelate compound, when an ink layer is formed, the elasticity and viscosity at high temperature can be increased, and both heat resistance and workability can be achieved. When a crosslinker other than a metal chelate compound is used, the elasticity becomes too high compared to the viscosity, that is, the ink layer tends to be too hard, so the processability at the time of compression molding cannot be secured, and the ink layer Cracks are likely to occur.

  In addition, when a cross-linking agent other than a metal chelate compound is used, since cross-linking starts from the time when the cross-linking agent is added, there is a problem that the pot life is short, and further, the pot life becomes shorter as the amount of the cross-linking agent increases. There is a problem of end. On the other hand, when a metal chelate compound is used as a crosslinking agent, crosslinking does not start from the time when the crosslinking agent is added, and the pot life is prolonged.

  Furthermore, since content of a metal chelate compound is 2 mass parts-20 mass parts with respect to 100 mass parts of (meth) acrylic-type polymers, when forming an ink layer, it can be compatible with heat resistance and workability.

  Specifically, since the content of the metal chelate compound is 2 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic polymer, it is possible to increase the crosslinking density at the time of crosslinking and suppress the occurrence of ink flow. Therefore, it is possible to provide an ink binder composition having excellent heat resistance when an ink layer is formed.

  Furthermore, since the content of the metal chelate compound is 20 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer, the crosslink density at the time of crosslinking does not become too high, and the ink layer is suppressed from becoming too hard. The Thereby, viscosity is ensured when the ink layer is formed, and the ink layer suitably follows the deformation of the substrate to be printed at the time of compression molding. Therefore, the processability at the time of compression molding is excellent, and the occurrence of cracks in the ink layer can be suppressed.

[(Meth) acrylic polymer]
The ink binder composition in the present invention has a structural unit (A) derived from a (meth) acrylic acid alkyl ester, a structural unit (B) derived from a monomer having a carboxy group, and a polar functional group other than the carboxy group. A structural unit derived from a monomer (C), wherein the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more based on the total structural units, and the structural unit The total of the content rate of (B) and the content rate of the said structural unit (C) is 8 mol% or more with respect to all the structural units, and the glass transition temperature contains the (meth) acrylic-type polymer which is 20 degreeC or more. . Thereby, both elasticity and viscosity at high temperatures can be increased, and both heat resistance and workability can be achieved.

<Constitutional unit derived from (meth) acrylic acid alkyl ester (A)>
The (meth) acrylic polymer used in the present invention contains a structural unit (A) derived from a (meth) acrylic acid alkyl ester. This structural unit (A) is the main component of the (meth) acrylic polymer.

  Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid alkyl esters in which the alkyl group is linear, branched or cyclic.

  Examples of the (meth) acrylic acid alkyl ester in which the alkyl group is linear or branched include (meth) acrylic acid alkyl esters in which the alkyl group has 1 to 20 carbon atoms, preferably carbon of the alkyl group. (Meth) acrylic acid alkyl ester having 1 to 12 carbon atoms, more preferably (meth) acrylic acid alkyl ester having 1 to 8 carbon atoms in the alkyl group.

  Specific examples of (meth) acrylic acid alkyl esters in which the alkyl group is linear or branched include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. I-propyl acid, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, (meth) ) Isodecyl acrylate, lauryl (meth) acrylate, n-dodecyl (meth) acrylate, tridecyl (meth) acrylate, Meth) acrylic acid stearyl. Of these, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable.

  Examples of the (meth) acrylic acid alkyl ester in which the alkyl group is cyclic include a (meth) acrylic acid alkyl ester having an aromatic ring structure or an alicyclic structure.

  Specific examples of the alkyl (meth) acrylate alkyl ester having a cyclic alkyl group include phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate. , (Meth) acrylic acid ethylene oxide (EO) modified cresol, (meth) acrylic acid ethylene oxide (EO) modified nonylphenol, (meth) acrylic acid biphenyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclopentanyl And isobornyl (meth) acrylate.

  In addition, as a (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkyl ester having a glass transition temperature of −40 ° C. or lower when a homopolymer and a homopolymer are used. ) It preferably contains an acrylic acid alkyl ester. By including the structural unit derived from these (meth) acrylic acid alkyl esters in the (meth) acrylic polymer, the (meth) acrylic polymer is formed so that the balance between heat resistance and workability when the ink layer is formed is improved. ) The glass transition temperature of the acrylic polymer can be adjusted. Examples of the (meth) acrylic acid alkyl ester having a glass transition temperature of −40 ° C. or lower when a homopolymer is used include n-butyl acrylate (−57 ° C.) and 2-ethylhexyl acrylate (−76 ° C.). Examples of the (meth) acrylic acid alkyl ester having a glass transition temperature of 50 ° C. or higher when a homopolymer is used include, for example, methyl methacrylate (103 ° C.).

  The content of the structural unit (A) in the (meth) acrylic polymer is not particularly limited, but it is 50 moles with respect to all structural units from the viewpoint of balancing heat resistance and workability when the ink layer is formed. % To 92 mol% is preferable, and 55 mol% to 80 mol% is preferable.

  The structural unit (A) derived from the (meth) acrylic acid alkyl ester in the (meth) acrylic polymer may be one type or two or more types. For example, the structural unit (A) may be a structural unit derived from at least one selected from the aforementioned (meth) acrylic acid alkyl esters.

<Structural Unit (B) Derived from Monomer Having Carboxy Group>
The (meth) acrylic polymer used in the present invention includes a structural unit (B) derived from a monomer having a carboxy group, and the content of the structural unit (B) is 3 mol% or more based on the total structural units.

  Specific examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, succinic acid monohydroxyethyl (meth) acrylate, and monohydroxyethyl maleate. (Meth) acrylate, monohydroxyethyl fumarate (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 1,2-dicarboxycyclohexane monohydroxyethyl (meth) acrylate, (meth) acrylic acid dimer, ω-carboxy -Polycaprolactone mono (meth) acrylate. Among these, acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone mono (meth) acrylate are preferable.

  The content of the structural unit (B) derived from the monomer having a carboxy group in the (meth) acrylic polymer is 4 mol% based on the total structural units from the viewpoint of further improving the heat resistance when the ink layer is formed. Preferably, it is 7 mol% or more, more preferably 10 mol% or more. Further, the content of the structural unit (B) is not particularly limited as long as it is 3 mol% or more. However, the processability when the ink layer is formed is suitably maintained, and other structural units, particularly the structural units (C ), It is preferably 30 mol% or less, more preferably 26 mol% or less.

  The structural unit (B) derived from the monomer having a carboxy group in the (meth) acrylic polymer may be one type or two or more types. For example, the structural unit (B) may be a structural unit derived from at least one selected from the above-described monomers having a carboxy group.

<Constitutional unit derived from monomer having polar functional group other than carboxy group (C)>
The (meth) acrylic polymer used in the present invention includes a structural unit (C) derived from a monomer having a polar functional group other than a carboxy group, and the content of the structural unit (C) is 3 mol with respect to all the structural units. % Or more.

  Examples of the monomer having a polar functional group other than a carboxy group include a monomer having a hydroxyl group, a monomer having a nitrogen atom, and a monomer having a glycidyl group, preferably a (meth) acrylic monomer having a hydroxyl group, a nitrogen atom And (meth) acrylic monomers having a glycidyl group.

  As the monomer having a hydroxyl group, for example, from the point that compatibility and copolymerization with other monomers are good, and adhesion to a substrate to be printed such as a transparent film is good. A hydroxyalkyl (meth) acrylate having 8 hydroxyalkyl groups is preferred, a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 to 5 carbon atoms is more preferred, and having a hydroxyalkyl group having 2 to 4 carbon atoms More preferred is hydroxyalkyl (meth) acrylate.

  Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylic acid 3-methyl-3-hydroxybutyl, (meth) acrylic acid 1,1-dimethyl-3-hydroxybutyl, (meth) acrylic acid 1,3-dimethyl-3-hydroxybutyl, (meth) acrylic 2,2,4-trimethyl-3-hydroxypentyl acid, 2-ethyl-3-hydroxyhexyl (meth) acrylate, glycerin mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate , Poly (ethylene glycol-propylene glycol Lumpur) mono (meth) acrylate, N- methylol acrylamide, allyl alcohol, methallyl alcohol. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.

  Specific examples of the monomer having a nitrogen atom include 2-aminoethyl (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, and 3-methacrylic acid 3- (Dimethylamino) propyl, N, N-dimethyl (meth) acrylamide, N, N-diethylacrylamide, N-ethyl, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide may be mentioned.

  Among the monomers having a nitrogen atom, a monomer having an amino group is preferable from the viewpoint that adhesion to a substrate to be printed is further enhanced when an ink layer is formed. For example, 2-aminoethyl (meth) acrylate, (meth ) 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl (meth) acrylate, and 3- (dimethylamino) propyl methacrylate. Of these, 2- (dimethylamino) ethyl (meth) acrylate and 2- (diethylamino) ethyl (meth) acrylate are preferable.

  Specific examples of the (meth) acrylic monomer having a glycidyl group include glycidyl (meth) acrylate.

  In the (meth) acrylic polymer, the content of the structural unit (C) derived from the monomer having a polar functional group other than the carboxy group increases the adhesion between the ink layer and a substrate to be printed such as a transparent film. Therefore, the content is preferably 5 mol% or more, more preferably 8 mol% or more, and further preferably 10 mol% or more with respect to all the structural units. Further, the content of the structural unit (C) is not particularly limited as long as it is 3 mol% or more, but it is 30 mol% or less from the viewpoint of balancing with other structural units, particularly the structural unit (B). Is preferable, and it is more preferable that it is 20 mol% or less.

  In the (meth) acrylic polymer, the content of the structural unit (C ′) derived from the monomer having a nitrogen atom (preferably a monomer having an amino group) increases the workability when the ink layer is formed. Therefore, it is preferably 0.3 mol% or more, more preferably 0.5 mol% or more with respect to all the structural units. Further, the content of the structural unit (C ′) is preferably 1.0 mol% or less from the viewpoint of workability during polymerization and ease of viscosity adjustment when used as an ink, and is preferably 0.8 mol%. The following is more preferable.

  The total content of the structural unit (B) and the content of the structural unit (C) in the (meth) acrylic polymer is 8 mol% or more with respect to all the structural units. Thereby, when an ink layer is formed, both elasticity and viscosity at high temperatures can be increased, and both heat resistance and workability can be achieved. Furthermore, the sum of the content of the structural unit (B) and the content of the structural unit (C) suitably maintains the heat resistance and processability when the ink layer is formed, and the structural unit (A) and the structural unit. From the viewpoint of balancing (B) and the structural unit (C), the content is preferably 50 mol% or less, more preferably 45 mol% or less, based on all the structural units.

  In the ink binder composition of the present invention, the content ratio of the structural unit (C) to the structural unit (B) (structural unit (C) / structural unit (B)) is 0.5 to 2. 0 is preferred. Thereby, when an ink layer is formed, the follow-up of the ink layer at the time of stretching becomes good, and heat resistance and workability are further improved.

  The (meth) acrylic polymer used in the present invention may contain structural units derived from other copolymerizable monomers. Examples of other copolymerizable monomers include aromatic vinyl monomers, vinyl cyanide monomers, vinyl carboxylate monomers, and various derivatives thereof. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene, vinyltoluene, and vinylpyridine. Examples of the vinyl cyanide monomer include acrylonitrile, Examples of the vinyl carboxylate monomer include vinyl formate, vinyl acetate, vinyl propionate, and “vinyl versatate” (trade name, vinyl neodecanoate).

  The weight average molecular weight (Mw) of the (meth) acrylic polymer used in the present invention is not particularly limited, but is preferably 5000 or more, more preferably 10,000 or more, from the viewpoint of enhancing the heat resistance when the ink layer is formed. More preferably 50000 or more. In addition, the weight average molecular weight (Mw) is preferably 1000000 or less, more preferably 500000 or less, and even more preferably 300000 or less, from the viewpoint of balancing heat resistance and workability when the ink layer is formed. The weight average molecular weight can be adjusted by the polymerization reaction temperature, time, the amount of organic solvent, and the like.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is a value measured by the following method.
(Measurement method of weight average molecular weight (Mw))
It measures according to following (1)-(3).
(1) A (meth) acrylic polymer solution is applied to a release film and dried at 100 ° C. for 2 minutes to obtain a film-like (meth) acrylic polymer.
(2) The film-like (meth) acrylic polymer obtained in (1) is dissolved in tetrahydrofuran so that the solid content is 0.2%.
(3) The weight average molecular weight (Mw) of the (meth) acrylic polymer is measured as a standard polystyrene conversion value using gel permeation chromatography (GPC) under the following conditions.
(conditions)
GPC: HLC-8220 GPC [manufactured by Tosoh Corporation]
Column: 4 TSK-GEL GMHXL used Mobile phase solvent: Tetrahydrofuran Flow rate: 0.6 ml / min
Column temperature: 40 ° C

  The glass transition temperature (Tg) of the (meth) acrylic polymer used in the present invention is 20 ° C. or higher. For this reason, the ink binder composition of the present invention can suppress the occurrence of ink flow when the ink layer is formed, and is excellent in heat resistance. Further, the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 30 ° C. or higher from the viewpoint of more suitably suppressing the occurrence of ink flow when the ink layer is formed and further improving heat resistance. 40 degreeC or more is more preferable.

  The glass transition temperature (Tg) of the (meth) acrylic polymer used in the present invention is 60 ° C. from the point that when the ink layer is formed, the followability of the ink layer at the time of stretching becomes better and the workability is further improved. The following is preferable, and 50 ° C. or lower is more preferable.

  The glass transition temperature (Tg) of the (meth) acrylic polymer is a value obtained by converting the absolute temperature (K) obtained by calculation of the following formula into Celsius temperature (° C.). The absolute temperature (K) can be converted into the Celsius temperature (° C.) by subtracting 273 from the absolute temperature (K), and the Celsius temperature (° C.) can be converted into the absolute temperature (° C.) by adding 273 to the Celsius temperature (° C.). K) can be converted.

Table absolute temperature (K) when in the _formula, Tg _1, Tg 2, ..... and Tg _n is the monomer 1, monomer 2, a ..... and monomer n of each monomer polymerized into a homopolymer Is the glass transition temperature. m ₁ , m ₂ ,... and _mn are the mole fractions of the respective monomers.

  The “glass transition temperature represented by the absolute temperature (K) when a homopolymer is used” is the glass transition temperature represented by the absolute temperature (K) of a homopolymer produced by polymerizing the monomer alone. Say. The glass transition temperature of the homopolymer was determined by using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., EXSTAR 6000) under a condition of 10 mg of a measurement sample and a heating rate of 10 ° C./min. Measurement is performed, and the inflection point of the obtained DSC curve is defined as the glass transition temperature of the homopolymer.

  The production method of the (meth) acrylic polymer used in the present invention is not particularly limited, and can be produced by polymerizing monomers by methods such as solution polymerization, emulsion polymerization and suspension polymerization. In preparing the ink binder composition of the present invention after production, solution polymerization is preferred because the treatment process can be performed relatively easily and in a short time.

  In solution polymerization, a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as necessary are generally charged in a polymerization tank, and the number is stirred in a nitrogen stream or at the reflux temperature of the organic solvent. A method such as heating for a period of time can be used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be adjusted to a desired value by adjusting reaction temperature, time, the amount of solvent, and the kind and amount of a catalyst, for example.

  Examples of the organic solvent for polymerization used in the production of the (meth) acrylic polymer include aromatic hydrocarbon compounds, aliphatic or alicyclic hydrocarbon compounds, ester compounds, ketone compounds, glycol ether compounds, alcohol compounds, and the like. Can be mentioned. These organic solvents may be used alone or in combination of two or more. Moreover, as a polymerization initiator, the organic peroxide and azo compound which can be used with a normal polymerization method are mentioned, for example.

[Metal chelate compounds]
The binder composition for ink in the present invention contains a metal chelate compound together with the above (meth) acrylic polymer, and the content of the metal chelate compound is 2 parts by mass to 100 parts by mass of the (meth) acrylic polymer. 20 parts by mass. Thereby, by cross-linking an acrylic polymer using a metal chelate compound, the elasticity and viscosity at high temperature can be increased, and both heat resistance and workability can be achieved.

  Although it will not specifically limit as a metal chelate compound if the effect of this invention is acquired, For example, an aluminum chelate compound, a titanium chelate compound, a zirconium chelate compound, and a cobalt chelate compound are mentioned. Among these, an aluminum chelate compound is preferable.

  Examples of the aluminum chelate compound include aluminum monoacetylacetonate bis (ethyl acetoacetate), aluminum tris (ethyl acetoacetate), and aluminum tris (acetylacetonate). Among these, aluminum monoacetylacetonate bis (ethyl acetoacetate) is preferable from the viewpoint of improving the balance between heat resistance and workability when the ink layer is formed.

  Moreover, as an aluminum chelate compound, you may use what is marketed, for example, Kawaken Fine Chemical Co., Ltd. aluminum chelate D, aluminum chelate A, and ALCH-TR are mentioned.

  In the ink binder composition of the present invention, the content of the metal chelate compound is not particularly limited as long as it is 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. From the point which raises the heat resistance of more, it is preferable that it is 5-20 mass parts with respect to 100 mass parts of (meth) acrylic-type polymers, and it is preferable that it is 7-20 mass parts.

[Organic solvent]
Moreover, the organic binder may be added to the binder composition for inks in this invention in order to improve the applicability | paintability with respect to to-be-printed substrates, such as a transparent film. The organic solvent is not particularly limited, and for example, hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, hydrocarbons represented by methylcyclohexane, dichloromethane, trichloroethane, trichloroethylene, tetrachloroethylene, dichloropropane, etc. Halogenated hydrocarbons, methanol, ethanol, propanol, isopropanol, butanol, isobutyl alcohol, alcohols typified by diacetone alcohol, ethers typified by diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, acetone, acetylacetone, methyl ethyl ketone , Ketones represented by methyl isobutyl ketone, isophorone, cyclohexanone, methyl acetate, ethyl acetate , Esters such as butyl acetate, isobutyl acetate, amyl acetate, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether acetate, polyols represented by propylene glycol monomethyl ether acetate, etc. Organic solvents such as derivatives thereof.

[Other ingredients]
In addition to the (meth) acrylic polymer, the metal chelate compound, and the organic solvent, the ink binder composition of the present invention includes a silane coupling agent and a crosslinking agent other than the metal chelate compound, as long as the effects of the present invention are obtained. Weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, antioxidants, ultraviolet absorbers, hindered amine compounds, and other light stabilizers may be appropriately contained.

  In the ink binder composition of the present invention, the gel fraction after crosslinking is preferably 73% or more, more preferably 80% or more, from the viewpoint of suppressing the occurrence of ink flow by increasing the crosslinking density at the time of crosslinking. % Or more is more preferable. In addition, the gel fraction after bridge | crosslinking is a ratio measured by the method as described in a following example, and is a ratio of a solvent insoluble part measured using ethyl acetate as an extraction solvent.

In the ink binder composition of the present invention, the storage elastic modulus (E ′) at 250 ° C. after crosslinking is preferably 4.0 × 10 ⁶ Pa or more in order to further increase the heat resistance when the ink layer is formed. 0.0 × 10 ⁶ Pa or more is more preferable, and 6.0 × 10 ⁶ Pa or more is more preferable. In the ink binder composition of the present invention, the storage elastic modulus (E ′) at 250 ° C. after crosslinking is preferably 3.0 × 10 ⁷ Pa or less, and more preferably 2.0 × 10 ⁷ Pa or less. The storage elastic modulus (E ′) is a value measured by the method described in the following examples.

In the ink binder composition of the present invention, the loss elastic modulus (E ″) at 250 ° C. after crosslinking is preferably 3.0 × 10 ⁵ Pa or more in order to further improve the workability when the ink layer is formed. 3.5 × 10 ⁵ Pa or more is more preferable, and 4.0 × 10 ⁵ Pa or more is more preferable. In the ink binder composition of the present invention, the loss elastic modulus (E ″) at 250 ° C. after crosslinking is preferably 9.0 × 10 ⁵ Pa or less, and more preferably 8.0 × 10 ⁵ Pa or less. . The loss elastic modulus (E ″) is a value measured by the method described in the following examples.

In the ink binder composition according to the present invention, the loss tangent at 250 ° C. (tan δ = E ″ / E ′) after crosslinking is 2 in order to balance heat resistance and processability when the ink layer is formed. 0 × 10 ^{−2 to} 2.0 × 10 ⁻¹ is preferable, and 2.0 × 10 ^{−2 to} 9.5 × 10 ⁻² is preferable.

[Binder for ink used for injection molding]
The ink binder used in the injection molding in the present invention is composed of the structural unit (A) derived from the (meth) acrylic acid alkyl ester, the structural unit (B) derived from the monomer having a carboxy group, and a polar functional group other than the carboxy group. A structural unit derived from a monomer having a group (C), and the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more with respect to all the structural units. (Meth) acrylic whose total of the content rate of the said structural unit (B) and the content rate of the said structural unit (C) is 8 mol% or more with respect to all the structural units, and whose glass transition temperature is 20 degreeC or more. System polymers. Thereby, when an ink layer is formed using the aforementioned metal chelate compound and an ink binder used for injection molding, both elasticity and viscosity at high temperatures can be increased, and heat resistance and workability can be improved. Can be compatible. This invention is different from the above-mentioned ink binder composition in the present invention in that it is used for injection molding and does not contain a metal chelate compound.

[Ink material set]
The ink material set in the present invention includes a structural unit (A) derived from (meth) acrylic acid alkyl ester, a structural unit (B) derived from a monomer having a carboxy group, and a monomer having a polar functional group other than the carboxy group. And the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more with respect to all the structural units, and the structural unit The total of the content rate of (B) and the content rate of the said structural unit (C) is 8 mol% or more with respect to all the structural units, and the glass transition temperature contains the (meth) acrylic-type polymer which is 20 degreeC or more. A first material and a second material including a metal chelate compound. When the ink layer is formed using the first material containing the (meth) acrylic polymer and the second material containing the metal chelate compound, both elasticity and viscosity at high temperature can be increased. Both heat resistance and workability can be achieved. This invention is different from the ink binder composition of the present invention described above in that it includes two materials, a material containing a (meth) acrylic polymer and a material containing a metal chelate compound.

〔ink〕
The ink in the present invention contains the first material and the second material in the aforementioned ink binder composition or the aforementioned ink material set, and an organic solvent. Thereby, when an ink layer is formed, both elasticity and viscosity at high temperature can be increased, and both heat resistance and workability can be achieved. The ink in the present invention may be used for a film for injection molding. For example, the ink may be printed on a film for injection molding and used for producing an injection molded product.

  The ink in the present invention may contain other components in the same manner as the above-described ink binder composition. The ink in the present invention may be a colored ink containing a colorant such as a pigment or a dye, or may be a clear ink containing no colorant.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

<Manufacture of (meth) acrylic polymer>
(Production Example 1)
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, methyl methacrylate (MMA) 12.2 parts by mass, n-butyl acrylate (BA) 11.5 parts by mass, acrylic acid (AA) 5.1 Part by mass, 5.5 parts by mass of 2-hydroxyethyl methacrylate (2HEMA), 100 parts by mass of butyl cellosolve acetate, and 0.02 parts by mass of 2,2′-azobis (2-methylpropionitrile) were mixed, The reactor was purged with nitrogen. Then, it heated up to 80 degreeC, stirring the obtained mixture. After maintaining the temperature for 0.5 hours, 23.3 parts by mass of methyl methacrylate (MMA), 22 parts by mass of n-butyl acrylate (BA), 9.9 parts by mass of acrylic acid (AA), 2-methacrylic acid 2- A mixed solution of 10.5 parts by mass of hydroxyethyl (2HEMA), 45 parts by mass of butyl cellosolve acetate and 0.15 parts by mass of 2,2′-azobis (2-methylpropionitrile) was successively added dropwise over 2.5 hours. After completion of the dropping, a polymerization reaction is performed for 1 hour, and a mixed solution of 15 parts by mass of butyl cellosolve acetate (ethylene glycol monobutyl ether acetate) and 0.34 parts by mass of 2,2′-azobis (2-methylpropionitrile) is added for 1 hour. It was dripped sequentially. After completion of the dropping, a polymerization reaction was further performed for 1.5 hours. The reaction mixture after the completion of the polymerization reaction was diluted with butyl cellosolve acetate to adjust the polymer solid content to 30% by mass. In this way, a (meth) acrylic polymer solution was obtained.

(Production Example 2)
In Production Example 2, when the (meth) acrylic polymer was produced, the monomer composition shown in Table 1 below was used, and the polymerization conditions were adjusted so that the glass transition temperature shown in Table 1 and the weight average molecular weight shown in Table 2 were obtained. Except for this, a solution of a (meth) acrylic polymer was obtained in the same manner as in Production Example 1. In Production Example 2, solutions of (meth) acrylic polymers having different weight average molecular weights as shown in Table 2 were prepared by adjusting the polymerization conditions.

(Production Example 3 to Production Example 24)
In Production Example 3 to Production Example 24, when producing a (meth) acrylic polymer, the monomer composition shown in Table 1 below was used, and polymerization was performed so that the glass transition temperature shown in Table 1 and the weight average molecular weight shown in Table 2 were obtained. A solution of a (meth) acrylic polymer was obtained in the same manner as in Production Example 1 except that the conditions were adjusted.

  In Table 1, nBMA is n-butyl methacrylate, EA is ethyl acrylate, 2EHA is 2-ethylhexyl acrylate, MAA is methacrylic acid, 2HEA is 2-hydroxyethyl acrylate, 4HBA is 4-hydroxybutyl acrylate , DEMA represents 2- (diethylamino) ethyl methacrylate, DMMA represents 2- (dimethylamino) ethyl methacrylate, and GMA represents glycidyl methacrylate. In Table 1, M5300 represents ω-carboxypolycaprolactone (n≈2) monoacrylate (product name: Aronix M-5300, manufactured by Toagosei Co., Ltd.).

  Here, in Production Example 1 to Production Example 21, the (meth) acrylic polymer is a structural unit (A) derived from a (meth) acrylic acid alkyl ester, a structural unit (B) derived from a monomer having a carboxy group, And a structural unit (C) derived from a monomer having a polar functional group other than a carboxy group, the content of the structural unit (B) and the content of the structural unit (C) are each 3 mol% or more, and the structural unit The sum total of the content rate of (B) and the content rate of a structural unit (C) was 8 mol% or more, and the glass transition temperature was 20 degreeC or more.

  On the other hand, in Production Example 22, the total content of the structural unit (B) and the content of the structural unit (C) is less than 8 mol%, and in Production Example 23, the content of the structural unit (B) and the structural unit. Both the content rates of (C) were less than 3 mol%, and the sum total of the content rate of a structural unit (B) and the content rate of a structural unit (C) was less than 8 mol%.

  Furthermore, in Production Example 24, the glass transition temperature of the (meth) acrylic polymer was less than 20 ° C.

  Table 1 below shows the monomer composition (mol%) when producing the (meth) acrylic polymer in Production Examples 1 to 24 and the Tg of the (meth) acrylic polymer produced in Production Examples 1 to 24. Show.

<Preparation of binder composition>
Example 1
333 parts by mass of the (meth) acrylic polymer solution obtained in Production Example 1 (100 parts by mass of polymer solid content of 30% by mass) and aluminum chelate D (Kawaken Fine Chemical Co., Ltd. aluminum chelate: aluminum mono) as the metal chelate compound 9.6 parts by mass of acetylacetonate bis (ethyl acetoacetate) 76 mass% isopropanol solution) and 9.6 parts by mass of acetylacetone were sufficiently stirred and mixed to prepare a binder composition. In addition, content of the metal chelate compound in a binder composition is 7.3 mass parts with respect to 100 mass parts of (meth) acrylic-type polymers.

(Examples 2 to 7)
In Examples 2 to 7, except that the (meth) acrylic polymer solution obtained in Production Example 2 to 4 was used instead of the (meth) acrylic polymer solution obtained in Production Example 1, respectively. A binder composition was prepared in the same manner as in Example 1.

(Example 8)
In Example 8, aluminum chelate A (Aluminum chelate manufactured by Kawaken Fine Chemical Co., Ltd .: aluminum tris (acetylacetonate)) was used in place of aluminum chelate D as the metal chelate compound. A binder composition was prepared.

Example 9
Example 9 was the same as Example 1 except that ALCH-TR (aluminum chelate: aluminum tris (ethyl acetoacetate) manufactured by Kawaken Fine Chemical Co., Ltd.) was used instead of aluminum chelate D as the metal chelate compound. A binder composition was prepared.

(Examples 10-23, 26-28)
In Examples 10-23 and 26-28, the (meth) acrylic polymer solution obtained in Production Example 5-21 was used instead of the (meth) acrylic polymer solution obtained in Production Example 1. Except for the points, a binder composition was prepared in the same manner as in Example 1.

(Examples 24 and 25)
In Example 24, except that the amount of the metal chelate compound was adjusted so that the content of the metal chelate compound in the binder composition was 2.3 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer, A binder composition was prepared in the same manner as in Example 1.
In Example 25, the amount of the metal chelate compound was adjusted so that the content of the metal chelate compound in the binder composition was 19.7 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. Prepared a binder composition in the same manner as in Example 1.

(Comparative Example 1)
In Comparative Example 1, in place of aluminum chelate D which is a metal chelate compound, coronate L-45E (TDI isocyanate manufactured by Nippon Polyurethane Industry Co., Ltd.) which is an isocyanate compound is used, and the content of the isocyanate compound in the binder composition A binder composition was prepared in the same manner as in Example 1 except that the amount of the isocyanate compound was adjusted so as to be 10.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer.

(Comparative Example 2)
In Comparative Example 2, in place of aluminum chelate D which is a metal chelate compound, TETRAD-CS which is an epoxy compound (epoxy crosslinking agent manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used, and the content of the epoxy compound in the binder composition A binder composition was prepared in the same manner as in Example 1 except that the amount of the epoxy compound was adjusted to 2.5 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer.

(Comparative Example 3)
In Comparative Example 3, except that the amount of the metal chelate compound was adjusted so that the content of the metal chelate compound in the binder composition was 1.8 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer, A binder composition was prepared in the same manner as in Example 1.

(Comparative Example 4)
In Comparative Example 4, except that the amount of the metal chelate compound was adjusted so that the content of the metal chelate compound in the binder composition was 22.0 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer, A binder composition was prepared in the same manner as in Example 1.

(Comparative Examples 5-7)
In Comparative Examples 5 to 7, except that the (meth) acrylic polymer solution obtained in Production Examples 22 to 24 was used instead of the (meth) acrylic polymer solution obtained in Production Example 1, respectively. A binder composition was prepared in the same manner as in Example 1.

<Preparation of binder sheet>
Using the binder compositions of the Examples and Comparative Examples obtained above, binder sheets were prepared according to the following procedure. First, the binder composition was applied to the release agent-treated surface of the release film surface-treated with a silicone release agent so that the coating amount after drying was 30 g / m ² . Subsequently, the release film after application of the binder composition was dried at 80 ° C. for 1 hour using a hot air circulation dryer, a binder layer was formed on the release film, and a binder sheet was produced.

  In Table 2 below, Mw and Tg of (meth) acrylic polymers used in Examples 1 to 28 and Comparative Examples 1 to 7 and measurement results of binder sheets in Examples 1 to 28 and Comparative Examples 1 to 7 And the evaluation results are shown. In addition, the mass part of Table 2 is the value of solid content conversion, and Mw and Tg of the (meth) acrylic-type polymer were calculated | required by the above-mentioned method.

<Method for measuring gel fraction>
The following operations (1) to (3) were performed, and the gel fraction (mass%) of the binder composition was calculated from the following formula.
(Formula) Gel fraction (mass%) = [(Z−X) / (Y−X)] × 100
X: Mass of wire mesh (g), Y: Mass of sample for extraction (total mass of wire mesh and binder) (g), Z: Mass of sample for extraction dried after immersion (total of insoluble content of wire mesh and binder) Mass) (g)
(1) After peeling off the release film on one side of the above binder sheet, it was wrapped in a 250 mesh wire net (100 mm × 100 mm) in which about 0.5 g of binder was precisely weighed to obtain a sample for extraction. The mass of the sample for extraction (total mass of wire mesh and binder) was measured with a precision balance.
(2) An extraction sample was placed in a glass bottle containing 80 g of ethyl acetate as an extraction solvent and immersed for 3 days.
(3) After the immersion, the sample for extraction was taken out, washed with a small amount of ethyl acetate, and dried at 120 ° C. for 24 hours. The mass of the extraction sample after drying (the total mass of the insoluble content of the wire mesh and the binder) was measured with a precision balance.

<Measurement method of viscoelasticity (E ', E'')>
The binder was cut from the above-mentioned binder sheet with a width of 10 mm × 20 mm, and the cut binder was folded in half to make a width of 5 mm, using a dynamic viscoelasticity measuring device Rheogel-E4000 manufactured by UBM Co. The storage elastic modulus (E ′) and the loss elastic modulus (E ″) were measured, and the loss tangent (tan δ = E ″ / E ′) was determined. Table 2 shows E ′, E ″, and tan δ when the temperature is 250 ° C.
Measurement length: 10mm
Measurement mode: Tensile Temperature condition: 10 ° C to 280 ° C
Temperature increase rate: 5 ° C / min
Frequency: 10Hz

<Method for evaluating heat resistance and workability>
Using the storage elastic modulus (E ′) and loss elastic modulus (E ″) obtained by the measurement method described above, the heat resistance and workability were evaluated according to the following criteria. In addition, if it was more than evaluation C, it was judged that it was excellent in heat resistance and workability.
≪Heat resistance≫
A: E ′ at 250 ° C. is 6.0 × 10 ⁶ Pa or more B: E ′ at 250 ° C. is 5.0 × 10 ⁶ Pa or more and less than 6.0 × 10 ⁶ Pa C: E at 250 ° C. 'Is 4.0 × 10 ⁶ Pa or more and less than 5.0 × 10 ⁶ Pa D: E at 250 ° C. is less than 4.0 × 10 ⁶ Pa << Processability >>
A: E ″ at 250 ° C. is 4.0 × 10 ⁵ Pa or more B: E ″ at 250 ° C. is 3.5 × 10 ⁵ Pa or more and less than 4.0 × 10 ⁵ Pa C: 250 ° C. E ″ of 3.0 × 10 ⁵ Pa or more and less than 3.5 × 10 ⁵ Pa D: E ″ at 250 ° C. is less than 3.0 × 10 ⁵ Pa

<Measurement method of pot life>
The binder composition just prepared as described above was used as a measurement sample, and the viscosity of the measurement sample was measured with a B-type viscometer. Thereafter, the measurement sample was sealed and allowed to stand at 23 ° C. for 24 hours, and then the viscosity of the measurement sample was again measured with a B-type viscometer. Using the ratio of the viscosity after standing for 24 hours to the initial viscosity, pot life was evaluated according to the following criteria.
≪Pot life≫
A: 1.2 times or less B: 1.2 times or more, 2 times or less C: more than 2 times

[result]
In Examples 1-28, in both heat resistance and workability, it was more than evaluation C, and was excellent in heat resistance and workability. On the other hand, in Comparative Examples 1-7, it was evaluation D in either heat resistance or workability, and either heat resistance or workability was inadequate.

Claims (11)

A structural unit (A) derived from a (meth) acrylic acid alkyl ester, a structural unit (B) derived from a monomer having a carboxy group, and a structural unit (C) derived from a monomer having a polar functional group other than a carboxy group wherein, the content of the structural unit (B) is, is 10 mol% or more based on all the structural units, the content of the structural unit (C) is, is 3 mol% or more based on the combined total of all structural units, the total content of the content and the structural unit (C) of the structural unit (B) is, and at 13 mol% or more based on all the structural units state, and are the glass transition temperature of 20 ° C. or higher, a weight-average molecular weight and There Ru der 50,000 (meth) acrylic polymer,
2 parts by mass to 20 parts by mass of a metal chelate compound with respect to 100 parts by mass of the (meth) acrylic polymer;
An ink binder composition comprising:   2. The ink binder composition according to claim 1, wherein a content ratio of the structural unit (C) to the structural unit (B) is 0.5 to 2.0 on a molar basis.   The ink binder composition according to claim 1, wherein the metal chelate compound is an aluminum chelate compound.   The ink binder composition according to claim 3, wherein the aluminum chelate compound is aluminum monoacetylacetonate bis (ethylacetoacetate).   As the (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkyl ester having a glass transition temperature of −40 ° C. or lower when the homopolymer is used and a glass transition temperature of 50 ° C. or higher when the homopolymer is used. The ink binder composition according to any one of claims 1 to 4, comprising an acrylic acid alkyl ester.   The ink binder composition according to any one of claims 1 to 5, comprising a monomer having an amino group as a monomer having a polar functional group other than the carboxy group.   The ink binder composition according to any one of claims 1 to 6, wherein the (meth) acrylic polymer has a glass transition temperature of 60 ° C or lower. A structural unit (A) derived from a (meth) acrylic acid alkyl ester, a structural unit (B) derived from a monomer having a carboxy group, and a structural unit (C) derived from a monomer having a polar functional group other than a carboxy group wherein and the content of the structural unit (B) is, is 10 mol% or more based on all the structural units, the content of the structural unit (C) is, is 3 mol% or more relative to all the structural units , the total content and the content of the constituent unit (C) of the structural unit (B) is, and at 13 mol% or more based on all the structural units state, and are the glass transition temperature of 20 ° C. or higher, a weight-average a first material with a molecular weight containing der Ru (meth) acrylic polymer to 50,000,
A second material comprising a metal chelate compound;
A material set for ink. The ink binder composition according to any one of claims 1 to 7, or the first material and the second material in the ink material set according to claim 8 ,
An organic solvent,
Containing ink. Furthermore, the ink of Claim 9 containing a coloring agent. The ink according to claim 9 or 10 , which is used for a film for injection molding.